JPS608057B2 - Water-dispersible metal powder composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to water-dispersible metal powder compositions.

More specifically, when used as a metal pigment in water-based paints, water-based adhesion agents, etc., it has excellent long-term storage stability, and when used as a metal powder, especially aluminum powder, as a foaming agent for lightweight cellular concrete, it has excellent initial storage stability. The present invention relates to a water-dispersible metal powder composition that has an excellent foaming retardation effect. In recent years, in the paint field, water-based paints that do not use organic agents are increasingly being used as a resource-saving and pollution-free measure.

Conventionally, metal powder pigments used in water-based paints are made of compositions that use saturated or unsaturated fatty acids such as stearic acid and oleic acid and their derivatives as surface treatment agents, and add surfactants to give water dispersibility. things are used. However, these water-dispersible metal powder pigments have the disadvantage of low storage stability in water-based paints, resulting in decreased pigment dispersibility and generation of large amounts of gas during storage. As a result, the properties of the paint are significantly impaired. Also,
When used as a foaming agent for lightweight cellular concrete, it does not contain organic solvents from the standpoint of environmental hygiene, and at the same time, it is a moisture-friendly metal powder composition that allows you to freely control the foaming start time and foaming speed during foam molding. is required.

In order to solve the problems of conventional water-dispersible metal pigments, the present inventors have conducted intensive studies and found that metal powder and an organic phosphate ester compound of 0.1 to 20% by weight based on the metal powder. It has been found that a water-dispersible metal powder composition containing as the main component has the best stability in aqueous paints.

As the metal powder used in the present invention, for example, powders of aluminum, copper, zinc, silver, malleable metals other than those mentioned above, alloys, etc. are used alone or in combination.

The metal powder is preferably scaly, and scaly metallic aluminum is particularly preferred. The purity of the metal powder is not particularly limited, but it is generally 99.9% for paints.
5% or more is used. Coarse particles are not preferable because they impair the appearance of the coating film, and those with a sieve residue of 0.5% or less in 149 degrees are preferable. The organic phosphate compound in the present invention adsorbs onto the surface of the metal powder, thereby providing a surface protection effect that suppresses the reaction of the metal powder.

A preferred organic phosphate compound is an organic phosphate compound represented by the general formula.

Here, R is an alkyl group having 6 to 24 carbon atoms, preferably 12 to 18 carbon atoms, an alkenyl group having 6 to 24 carbon atoms, preferably 12 to 18 carbon atoms, or an alkenyl group having 6 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
represents an aryl group containing one or more alkyl substituents having 8 carbon atoms or alkenyl substituents having 6 to 24 carbon atoms, preferably 12 to 18 carbon atoms, and A represents an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; m is 0-20, preferably 0-20
10, more preferably 2 to 8, and R and R2 may be the same or different, hydrogen, an alkyl group, an alkenyl group, an aryl group, or R-(OA)m
(where R, A and m are as indicated above). Examples of the alkyl group or alkenyl group in R, R., R2 include octyl, decyl, lauryl,
Cetyl, stearyl, oleyl, hexadecyl, octadecyl and the like are preferred. Preferred aryl groups for R, R4, and R2 include, for example, octylphenyl, nonylphenyl, dodecylphenyl, dinonylphenyl, and the like.

As A, ethylene and propylene are preferable. Specific compounds include alkyl, alkenyl, and
Preferred are aryl esters, alkyl, alkenyl, and esters obtained by adding ethylene oxide to an aryl group.

The phosphate ester may be mono-, di- or triester, or a mixture thereof. Alternatively, it may be a mixture of different types of phosphate esters. Furthermore, since these organic phosphate ester compounds exhibit acidity in aqueous solution, they can be added to ammonium, sodium hydroxide, potassium hydroxide, dibutylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, and morpholin. It can be used after being neutralized with an inorganic or organic basic substance.

The organic phosphate ester compound has a ratio of 0.1 to the metal powder.
It is used in the range of -2% by weight, preferably 1-1% by weight. Here, if the amount of the organic phosphate ester compound used is less than 0.1% by weight, the surface protection effect will be small, and if it exceeds 2% by weight, the water resistance of the coating strength obtained from the water-based paint obtained by acidifying the composition will decrease. It tends to reduce the There are no particular limitations on the method of adding the organic phosphate ester compound to the metal powder.

In general, scaly metal powder is produced by adding metal particles and a lubricant to improve grinding efficiency into a grinder such as a ball mill. For example, wet grinding in an organic solvent or a nitrogen atmosphere is used. Dry crushing methods are used. As lubricants at this time, saturated or unsaturated fatty acids, aliphatic amines, metal salts of fatty acids, etc. are generally used, and these are also surface treatment agents that adsorb to the surface of the metal powder and provide a surface protection effect. The organic phosphate ester compound can be used alone or in combination with these fatty acids or fatty acid derivatives. On the other hand, an organic phosphate ester compound is post-added together with water and a surfactant for imparting water dispersibility to a metal powder that has already been surface-treated using a fatty acid or a fatty acid conductor. You can also do it.

In the present invention, the surfactant for making the product water-soluble is not particularly limited, but it is preferable to use a nonionic surfactant from the viewpoint of storage stability.

Examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, and polyethylene glycol fatty acid ester. These are added in the mixing step of forming a paste of the metal powder together with the organic phosphate ester compound and the water of the dispersed soot. If necessary, various additives can be used in combination with the composition of the present invention. When a water-dispersible metal powder paste containing a metal powder and an organic phosphate ester compound as a basic composition and further containing a nonionic surfactant and water is used as a pigment for a water-based paint, it is extremely well dispersed in the paint. Even after long-term storage, the paint was chemically stable with no hydrogen gas generation or pigment aggregation, and there was almost no change in the paint properties. Furthermore, when used as a foaming agent for lightweight cellular concrete, it has become possible to freely control the foaming start time and foaming speed during foam molding. The water-dispersible I-type metal powder composition of the present invention can include countless combinations, and some representative ones will be described below with reference to Examples.

Example 1, Comparative Example 1 A mixture of granular aluminum powder 10k9 and mineral spirit 10k9 containing 5% by weight of stearic acid was ground in a ball mill for 8 hours, then mineral spirit 20k
After diluting by adding 9, transfer to a slurry tank and filter with a filter press.

The filter press cake thus obtained has a heating residue of 95% by weight and mineral spirit of 5% by weight.
The sieve residue in 149 pieces of aluminum powder was 0.
It was less than 1%. This filter press cake 100
A predetermined amount of a predetermined organic phosphate ester compound and a nonionic surfactant as shown in Table 1 are mixed with the weight part, and water is added so that the heating residue becomes 65% to obtain water-dispersible aluminum. A paste was prepared.

For comparison with the present invention, a water-dispersible aluminum paste with a heating residue of 65% was prepared in exactly the same manner using the known diammonium IJ acid as a surface treatment agent in Japanese Patent Publication No. 36-1981-1 Gisoshi No. 4. did. The water dispersibility, water stability, and long-term storage stability of the obtained aluminum paste were investigated as aluminum paste properties.
Furthermore, the properties of the paint and film when used in a water-based paint were investigated, and the results are shown in Table 1.

The test method used was as follows. [Properties of aluminum paste] {1) Water-dispersible Sample 3 samples were taken into a 50 mm Nessler tube, and a portion of the sample was added to pre-disperse.

After that, water was added up to the 50-degree mark, and after stirring well, the mixture was allowed to settle down and after 5 minutes had elapsed, the dispersion state of the aluminum particles was visually determined. ■ Water stability Using the experimental equipment shown in Figure 1, collect aluminum base for 20 minutes (residue on heating: 65%) into a 200 mm Erlenmeyer flask, add 100 mm of ion-exchanged water, and shake vigorously to disperse the sample. .

Attach a female pipette with a rubber stopper and immerse it in a 50qo constant temperature bath, and observe the state of gas generation after leaving it for two periods. '31
Place the shelf-stable aluminum paste in a 500' glass container;
Examine the properties after storage for 6 months at room temperature.

[Paint and coating properties] A water-soluble acrylic melamine resin coating was prepared using the following formulation, and the dispersion stability, storage stability, and coating appearance of the aluminum paste sample were evaluated.

Test aluminum paste (heated residue: 65%) 13. 370.0 parts by weight Water-soluble acrylic resin (heating residue 50%) Water-soluble melamine resin (heating residue 50%) 100. Parts by weight of deionized water 490. Mother weight part 973. Part by weight [1] Dispersion stability of aluminum pigment The aqueous metallic paint with the above formulation was left at room temperature for 3 months, and the dispersion stability was evaluated by the JISK 5400 4th scale gauge method.

'2} Gas generation from paint Using the experimental apparatus shown in Figure 1, a sample paint 100' was placed in a 200' Erlenmeyer flask, and the state of gas generation was observed after leaving it at 50°C for 20 hours.

'3} After blending the paint film appearance, the paint film was painted immediately and left at room temperature for 3 months. Tokoro Yag SK Mimimi ￥to is also a female song Spelling out half delicious earth ten l! Earth + li cloud spirit melting quantity 轡" tide sardines.

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Example 2, Comparative Example 2 A mixture of granular aluminum powder 10k9 and mineral spirit 10k9 containing 5% by weight of oleic acid was ground in a ball mill for 8 hours, then mineral spirit 20k9
After adding and diluting, transfer to a slurry tank and filter with a filter press.

The filter press cake thus obtained had a heating residue of 96% by weight and mineral spirit of 4% by weight.
The sieve residue in 149 pieces of aluminum powder was 0.
It was less than 1%. This filter press cake 100
To the weight part, 3 parts by weight of lauryl phosphate as an organic phosphate ester compound, 3 parts by weight of polyoxyethylene oleyl ether as a water dispersant, and a predetermined amount of water were added, and the mixture was uniformly heated at 40 oo for about 40 minutes. By kneading, a water-reducing aluminum paste with a heating residue of 65% was obtained.

For comparison with the present invention, a water-dispersible aluminum paste with a heating residue of 65% was prepared by carrying out exactly the same operation without adding lauryl phosphate. The physical properties of the base and the coating performance of the obtained aluminum paste were examined in the same manner as in Example 1. The results are shown in Table 2. Example 3
, Comparative Example 3 A mixture of granular aluminum powder 10k9 and mineral spirit 10k9 containing 6% by weight of polyoxyethylene (additional mole number 6 moles) stearyl ether phosphate as an organic phosphate ester compound was ground in a ball mill for 8 hours. Then, after diluting by adding mineral spirit 20k9, it is transferred to a slurry tank and filtered with a filter press.

The filter press cake thus obtained has a heating residue of 95% by weight and mineral spirit of 5% by weight.
The sieve residue in 149 pieces was less than 1%. Ethyl cellosolve was added to this filter press cake so that the heating residue was 65%, and the mixture was uniformly kneaded at 40° C. for about 40 minutes to obtain a water-dispersible aluminum paste. For comparison with the present invention, the same procedure was performed and heated, except that oleic acid was used instead of the organic phosphate ester compound to crush it into powder, and polyoxyethylene oleyl ether was added to achieve water dispersion. A moisture content aluminum paste with a residual content of 65% was prepared. The physical properties and paint performance of the obtained aluminum paste were examined in the same manner as in Example 1. The results are shown in Table 2. Example 4, Comparative Example 4 A mixture of granular zinc powder 15k9 and mineral spirit 10k9 containing 5% by weight of polyoxyethylene (additional mole number 6 moles) stearyl ether phosphate as an organic phosphate ester compound was heated in a ball mill. The mixture was ground for a time, then diluted with mineral spirit 20k9, transferred to a slurry tassock, and filtered through a filter press.

The filter press cake thus obtained has a heating residue of 9% by weight of mineral spirit and 1% by weight of mineral spirit;
The sieve residue in 149 pieces was less than 1%. Ethyl cellosolve was added to this filter press cake so that the heating residue was 65%, and the mixture was mixed uniformly at 40° C. for about 4 minutes to obtain a water-dispersible zinc paste.

For comparison with the present invention, the above-mentioned organic phosphoric acid ester compound Kawakiriko oleic acid was used, and the other operations were exactly the same. A filter press cake with a sieve residue of 1% or less was obtained. This filter press cake 1
Add 3 parts by weight of polyoxyethylene oleyl ether and a predetermined amount of ethyl cellosolve as a water dispersant to 00 parts by weight, and uniformly knead at 4000 for about 40 minutes to obtain a water dispersibility with heating residue of 65%. A zinc paste was obtained.

Example 1 for these obtained zinc nium pastes
In the same way as above, we investigated the physical properties of the paste and the performance of the paint.

The results are shown in Table 2. Example 5, Comparative Example 5 Granular steel powder 15k9, mineral spirit 1 containing 5% by weight of polyoxyethylene (additional mole number 6 moles) stearyl ether phosphate as an organic phosphate ester compound
The 0k9 mixture is ground in a ball mill for 8 hours, then diluted with mineral spirit 20k9, transferred to a slurry tank, and filtered through a filter press.

The filter press cake thus obtained contained 85% by weight of heating residue and 15% by weight of mineral spirit, and the sieve residue at 149 mm was less than 1%. To this filter press cake, add ethyl cellosolve so that the heating residue becomes 65%,
■A moisture-friendly steel base was obtained by uniformly mixing wires between the wires.

For comparison with the present invention, oleic acid was used instead of the organic phosphoric acid ester compound, and the same procedure was carried out except that the heating residue was 85% by weight, mineral spirit was 15% by weight, and the sieve residue in 149r was A filter press cake of less than 1% was obtained. This filter press cake 1
To 00 parts by weight, 3 parts by weight of polyoxyethylene oleyl ether and a predetermined amount of ethyl cellosolve were added as a water dispersant, and the mixture was uniformly mixed at 4000 for about 40 minutes until the heat residue was 65%. A water-dispersible copper powder base was obtained.

Example 1 about these obtained copper powder nium bases
In the same way as above, we investigated the physical properties of the paste and the performance of the paint. The results are shown in Table 2. Example 6 A lightweight product consisting of 66 parts of quicklime powder (3.2% on an 88mm sieve), 204 parts of poppy seeds, stone powder (30% on an 88A sieve, 45% on a 44mm sieve), and 17 anchors of water. An organic phosphate ester compound was added and mixed with 0.25 part of aluminum powder to a foamed concrete slurry in the proportions shown in Table 3, and the results shown in Table 3 and FIG. 1 were obtained.

In FIG. 1, the horizontal axis shows the time after no aluminum powder was added, and the vertical axis shows the expansion rate of the mud bran (the percentage after expansion relative to the volume of the mud bran before expansion). From the results in Table 3 and Figure 2, in mud competition 1 without adding organic phosphate ester compounds,
When aluminum powder is added, it begins to expand immediately, and
After a few minutes, approximately 1/2 of the final expansion volume is reached. As the amount of the organic phosphate ester compound added increases, the initial foaming start time becomes longer, and the effect of suppressing the reaction of the aluminum/nium powder is clearly observed, but when the amount added is 7.5×10-2
It was found that as the number of mud increases, the foaming efficiency decreases. As described above, the present invention is a lightweight cellular concrete third
By adding an organic phosphate ester compound to muddy acid together with a foaming agent, it is possible to delay the expansion of muddy acid due to hydrogen gas. Also, lightweight aerated concrete can be produced industrially with great advantage.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the test apparatus used for the water stability test. FIG. 2 is a diagram showing a mortar expansion coefficient curve. 1...Mespivet, 2...Rubber stopper, 3...Warm bath, 4...Sample. Purple l figure 2

Claims (1)

[Claims] 1. 0.1 to 20% by weight based on metal powder and metal powder
A water-dispersible metal powder composition comprising an organic phosphate compound represented by the following general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R is an alkyl group with 6 to 24 carbon atoms, 6 carbon atoms
~24 alkenyl group, an alkyl substituent having 6 to 24 carbon atoms, or an aryl group containing one or more alkenyl substituents having 6 to 24 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and m is 0 to 20, R_1 and R_
5 may be the same or different and represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or R-(OA
)_m (where R, A and m are as indicated above). 2. The water-dispersible metal powder composition according to claim 1, wherein the metal powder is at least one selected from the group consisting of aluminum, copper, zinc, brass, and other malleable metals and alloys. thing. 3. The water-dispersible metal powder composition according to claim 1, wherein the organic phosphate ester compound is neutralized with a basic substance.